Darcy's law‐based model for wicking in paper‐like swelling porous media

The wicking of liquid into a paper‐like swelling porous medium made from cellulose and superabsorbent fibers was modeled using Darcy's law. The work is built on a previous study in which the Washburn equation, modified to account for swelling, was used to predict wicking in a composite of cellulose and superabsorbent fibers. In a new wicking model proposed here, Darcy's law for flow in porous media is coupled with the mass conservation equation containing an added sink or source term to account for matrix swelling and liquid absorption. The wicking‐rate predicted by the new model compares well with the previous experimental data, as well as the modified Washburn equation predictions. The effectiveness of various permeability models used with the new wicking model is also investigated. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Prediction of dye concentrations in a three‐component dye mixture solution by a PCA‐derivative spectrophotometry technique

Derivative spectrophotometry is one of the most important techniques that can be used to determine the dye concentration. In addition, principal component analysis (PCA) is a linear method to condense the dimensionality of large numbers of absorbance spectra. In this work, PCA and derivative spectrophotometry techniques are used to improve the accuracy of Beer's law prediction of the concentrations in three‐component dye mixtures. The performance of the new method is compared with the normal Beer's law by calculation absolute error, relative error, and ternary relative error of prediction. As obtained results indicate, the prediction accuracy of dye concentration prediction in PCA‐derivative spectrophotometry method is higher than normal Beer's law method. © 2009 Wiley Periodicals, Inc., Col Res Appl, 2010.     

Fick's First Law of Diffusion and Binary Gas Separation by Hollow‐Fiber Asymmetric Membrane

For calculating mass transfer through a hollow‐fiber asymmetric membrane, a fundamentally new theoretical method based on Fick's first law of diffusion is proposed. The main features of this method, and the ones currently used for the same purpose, have been compared. The current methods, also based on Fick's first law of diffusion, are shown to be theoretically less than adequate. Recommendations are given for the practical implementation of the new method.     

Using field theory to measure surface resistivity of high-resistance polymeric films

Theoretical expressions based on Ohm's law for field theory were derived to measure surface resistivity of high-resistance polymer films using parallel plate and concentric circular electrodes. Experimental measurements of resistivity were compared to experimental measurements using conventional expressions based on Ohm's law for circuit theory. Expressions based on Ohm's law for circuit theory were found to be inadequate for measuring surface resistivity. The surface resistivity of high-resistance films can be accurately measured if electric field theory is used to include the effects of electrode structure, if relative humidity (RH) and temperature are controlled, if the level of applied voltage is limited, and if the measuring system is shielded from extraneous electric and magnetic fields. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2856–2862, 2001     

Applying alpha‐phenacyl chloride to the enantioselective reduction of ethyl 2‐oxo‐4‐phenylbutyrate with baker's yeast

BACKGROUND: The enantioselectivity of reduction of ethyl 2‐oxo‐4‐phenylbutyrate (EOPB) to synthesize ethyl (R)‐2‐hydroxy‐4‐phenylbutyrate ((R)‐EHPB) catalyzed with baker's yeast in diethyl ether can be improved by the introduction of alpha‐phenacyl chloride (PC). However, the toxicity of PC to the yeast results in a decrease in the catalytic activity of yeast. In order to overcome this limitation, four strategies for PC addition were designed. The effect of PC on the catalytic behavior of baker's yeast was studied using spectrum analysis of alcohol dehydrogenase from yeast (YADH). RESULTS: After being pretreated with PC according to Strategy 4, the pretreated baker's yeast possessed good catalytic activity and enantioselectivity for the reduction of EOPB to produce (R)‐EHPB. Under the optimum pretreatment conditions, the conversion of EOPB, the yield of EHPB and the enantiomeric excess of (R)‐EHPB reached 96%, 90% and 92%, respectively. Significant changes were observed in the UV absorption and fluorescence spectra of the YADH from the yeast pretreated by PC. CONCLUSION: The change of catalytic behavior of yeast after the pretreatment was probably caused by an interaction between yeast and PC. The reactive halomethyl group in PC molecule plays a key role for the interaction. Copyright © 2008 Society of Chemical Industry     

Structure and optical investigation of the effect of electron beam‐irradiation in poly‐allyl‐diglycol‐carbonate

The effect of electron beam irradiation on the structural and optical properties of Poly‐Allyl‐Diglycol‐Carbonate CR‐39 solid state nuclear track detector was investigated. Samples from CR‐39 detector were irradiated with electron beam with doses at levels between 10 and 140 kGy. The structural and optical modifications in the electron beam irradiated CR‐39 samples have been studied as a function of dose using different characterization techniques such as FTIR spectroscopy, Vickers hardness, refractive index and color difference measurements. The electron beam irradiation in the dose range 25–140 kGy led to a more compact structure of CR‐39 polymer, which resulted in an improvement in its hardness with an increase in the refractive index. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Darcy's law for two‐dimensional flows: Singularities at corners and a new class of models

As is known, Darcy's model for fluid flows in isotropic homogeneous porous media gives rise to singularities in the velocity field for essentially two‐dimensional flow configuration, like flows over corners. Considering this problem from the modeling viewpoint, this study aims at removing this singularity, which cannot be regularized via conventional generalizations of the Darcy model, like Brinkman's equation, without sacrificing Darcy's law itself for unidirectional flows where its validity is well established experimentally. The key idea is that as confirmed by a simple analogy, the permeability of a porous matrix with respect to flow is not a constant independent of the flow but a function of the flow field (its scalar invariants), decreasing as the curvature of the streamlines increases. This introduces a completely new class of models where the flow field and the permeability field are linked and, in particular problems, have to be found simultaneously. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

Controlled release of aminophylline from poly (N‐isopropylacrylamide‐co‐itaconic acid) hydrogels

N‐Isopropylacrylamide (NIPA) has been copolymerized with itaconic acid (IA) in the presence of N,N‐methylenebisacrylamide (BIS) as crosslinker. The swelling capacity and the release rate of aminophylline at 37 °C are reported. Maximum equilibrium swelling increases as the itaconic acid content in the hydrogel increases. The experimental data suggest clearly that the swelling process obeys second‐order kinetics. According to this, the kinetic constant, k, and the maximum equilibrium swelling, W_∞, have been calculated. Drug release from fully swollen hydrogels follows Fick's law closely, but deviates from it for xerogels. © 2001 Society of Chemical Industry     

Spontaneous imbibition of liquids in glass‐fiber wicks. Part I: Usefulness of a sharp‐front approach

Spontaneous imbibition of a liquid into glass‐fiber wicks is modeled using the single‐phase Darcy's law after assuming a sharp flow‐front marked by full saturation behind the front occurring in a transversely isotropic porous medium. An analytical expression for the height of the wicking flow‐front as a function of time is tested through comprehensive experiments involving using eight different wicks and one oil as the wicking liquid. A good fit with experimental data is obtained without using any fitting parameter. The contact‐angle is observed to be important for the success of the model—lower contact angle cases marked by higher capillary pressures were predicted the best. The proposed model provides a nice upper bound for all the wicks, thereby establishing its potential as a good tool to predict liquid absorption in glass‐fiber wicks. However, the sharp‐front model is unable to explain region of partial saturation, thereby necessitating the development of part II of this article series (Zarandi and Pillai, Spontaneous Imbibition of Liquid in Glass fiber wicks. Part II: Validation of a Diffuse‐Front Model. AIChE J, 64: 306–315, 2018) using Richard's equation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 294–305, 2018     

Grassmann's laws and individual color‐matching functions for non‐spectral primaries evaluated by maximum saturation technique in foveal vision

Over time, much work has been carried out to ascertain the validity of Grassmann's laws, Abney's law, CIE standard color‐matching functions and, up to now, no definitive answer has been given. Some of the phenomena subject of this debate are considered. An apparatus for color matching in 1.8° visual field has been realized with two sets of primary lights with broad spectral bands. This kind of primaries is the great difference with respect to other laboratories because it allows an indirect check of the Grassmann additivity law on the basis of the spectra and individual color‐matching functions by evaluating: (1) the tristimulus values of the primary lights; (2) the transformation matrices between the two reference frames defined by the two primary sets; and (3) the tristimulus values associated to all the pairs of matching lights in the bipartite field produced in the evaluation of the two sets of color‐matching function. The discrepancies of the data resulting in the check (1) and (2) are all compatible with the range defined by the uncertainty propagation of the individual color‐matching functions. In the check (3) fifteen tristimulus values over 18 have a discrepancy lower than one standard uncertainty. Grassmann's proportionality law is checked directly by reducing the matching lights with a neutral filter and holds true. © 2008 Wiley Periodicals, Inc. Col Res Appl, 33, 271–281, 2008.     

Enhancement in thermoelectric properties using a P‐type and N‐type thin‐film device structure

In this study, we have fabricated thermoelectric devices with p‐type and n‐type conducting polymers and research the effect of device structure with the thermoelectric properties. It was found that the p‐type and n‐type structure greatly enhances the device's electrical conductivity due to separated charge carrier channels, but the Seebeck coefficient was reduced due to the increase of charge density by doping. Photoexcitation can improve the device's thermoelectric properties and can increase the Seebeck coefficient and electrical conductivity with increasing doping concentration simultaneously. The increases in both properties are due to the phonon–electron coupling effect: the concentration of electrons and holes are increased under illumination, and the phonon component of the heat flux can be reduced by phonon scattering. Consequently, the thermoelectric device structure can improve the efficiency of thermoelectric conversion. The P3HT:PCBM devices demonstrate a significant enhancement in the power factor (PF = S²σ), with a maximum value of ZT = 0.5 at 147°C, in which the PF value (34.8 μV/cm K²) is bigger than Bi₂Te₃/Sb₂Te₃ superlattice devices at room temperature. POLYM. COMPOS., 34:1728–1734, 2013. © 2013 Society of Plastics Engineers     

Compatibilizing effect of starch‐grafted‐poly(L‐lactide) on the poly(ε‐caprolactone)/starch composites

The poly(ε‐caprolactone) (PCL)/starch blends were prepared with a coextruder by using the starch grafted PLLA copolymer (St‐g‐PLLA) as compatibilizers. The thermal, mechanical, thermo‐mechanical, and morphological characterizations were performed to show the better performance of these blends compared with the virgin PCL/starch blend without the compatibilizer. Interfacial adhesion between PCL matrix and starch dispersion phases dominated by the compatibilizing effects of the St‐g‐PLLA copolymers was significantly improved. Mechanical and other physical properties were correlated with the compatibilizing effect of the St‐g‐PLLA copolymer. With the addition of starch acted as rigid filler, the Young's modulus of the PCL/starch blends with or without compatibilizer all increased, and the strength and elongation were decreased compared with pure PCL. Whereas when St‐g‐PLLA added into the blend, starch and PCL, the properties of the blends were improved markedly. The 50/50 composite of PCL/starch compatibilized by 10% St‐g‐PLLA gave a tensile strength of 16.6 MPa and Young's modulus of 996 MPa, respectively, vs. 8.0 MPa and 597 MPa, respectively, for the simple 50/50 blend of PCL/starch. At the same time, the storage modulus of compatibilized blends improved to 2940 MPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of new poly(amide‐imide)s based on 1,3‐bis[4,4'‐(trimellitimido) phenoxy] propane and aromatic diamines

Six new poly(amide‐imide)s 8a–f containing trimethylene moiety in the main chain were synthesized by the polycondensation reactions of 1,3‐bis[4,4'‐(trimellitimido) phenoxy] propane 6 with six different aromatic diamines 7a–f in a medium constituting N‐methyl‐2‐pyrrolidone, triphenylphosphite, CaCl₂, and pyridine as condensing agents. The polycondensation reaction produced a series of novel poly(amide‐imide)s 8a–f in high yields with inherent viscosities between 0.35 and 0.63 dL/g. The resulting poly(amide‐imide)s were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis (TGA and DTG), solubility tests, and FTIR spectroscopy. 1,3‐Bis[4,4'‐(trimellitimido) phenoxy] propane 6 as a new monomer containing trimethylene moiety was synthesized using a three‐step reaction. At first 1,3‐bis[4,4'‐nitrophenoxy] propane 3 was prepared by the reaction of 4‐nitrophenol 1 with 1,3‐dibromo propane 2 in DMF solution . Then, dinitro 3 was reduced to 1,3‐bis[4,4'‐aminophenoxy] propane 4 by using a solution of sodium sulfite in ethanol. Finally, 1,3‐bis[4,4'‐(trimellitimido) phenoxy] propane 6 was prepared by the reaction of one equivalent diamine 4 with two equivalents of trimellitic anhydride 5 in a mixture of acetic acid‐pyridine (3 : 2). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A Ferroconcrete‐Like All‐Organic Nanocomposite Exhibiting Improved Mechanical Property,High Breakdown Strength,and High Energy Efficiency

Polymer‐based nanocomposite dielectrics with high energy storage capacity are crucial enablers for numerous applications in modern electronic and electrical industries. The energy density of parallel plate capacitors is determined by breakdown strength and dielectric permittivity of the inner dielectrics. Poly(vinylidene fluoride‐trifluoroethylene‐chlorofluoroethylene) (P(VDF‐TrFE‐CFE)), with the highest permittivity among all the dielectric polymers, is a promising candidate for high energy density capacitors. However, its relatively low breakdown strength and energy efficiency restrict the applications. In this work, a new method combining combinatorial‐electrospinning and hot‐pressing is proposed to fabricate P(VDF‐TrFE‐CFE)‐based all‐organic dielectrics with ferroconcrete‐like structure. In this structure, continuous fibers of polysulfone (PSF) with high Young's modulus act as tough scaffold to improve the mechanical properties of nanocomposites, and an over 750% enhancement of Young's modulus is obtained. The enhanced mechanical properties bring about significant improvement in Weibull breakdown strength to 485 MV m^?1, more than 50% higher than neat terpolymer. Furthermore, the suppressed leakage current and conduction loss, and hence the improved discharge energy efficiency under moderate electric field, are achieved due to the high insulation of PSF and its interfacial restriction on space charge mobility.     

Free‐volume microprobe study of iodine diffusion in polymers

The effect of iodine sorption on the free‐volume of three polymers, namely, acrylonitrile–butadiene–styrene, poly(ethylene terephthalate) and polycarbonate have been investigated by the positron annihilation lifetime technique. Diffusion coefficients have been evaluated from the sorption curves using Crank's solution for Fick's second law of diffusion. The positron results are explained in terms of iodine filling the free‐volume holes, swelling and conformational changes. It has also been found that the diffusion process in acrylonitrile–butadiene–styrene and poly(ethylene terephthalate) deviates from Fick's law of diffusion whereas in polycarbonate, the diffusion process obeys Fick's law. Further, for polymers in which diffusion deviates from Fick's law, the sorption process has been separated into diffusion‐controlled (Fickian) and relaxation‐controlled (non‐Fickian) parts using the dual‐mode sorption model. Interestingly, the present results show that the polymers which deviate from Fickian diffusion also deviate from Fujita's free‐volume theory of diffusion and vice versa. The positron results also indicate that sorbed iodine in the polymer acts as an inhibitor of ortho‐positronium. © 2001 Society of Chemical Industry     

The Role of Aluminum in the Detonation and Post‐Detonation Expansion of Selected Cast HMX‐Based Explosives

In order to improve understanding of how aluminum contributes in non‐ideal explosive mixtures, cast‐cured formulations have been analyzed in a series of cylinder tests and plate‐pushing experiments. This study describes the contribution of 15 % aluminum (median size of 3.2 μm) vs. lithium fluoride (an inert substitute for aluminum; <5 μm) in cast‐cured HMX formulations in different temporal regimes. Small cylinder tests were performed to analyze the detonation and wall velocities (1–20 μs) for these formulations. Near‐field blast effects of 58 mm diameter spherical charges were measured at 152 mm and 254 mm using steel plate acceleration. Pressure measurements at 1.52 m gave information about free‐field pressure at several milliseconds. While the observed detonation velocities for all formulations were within uncertainty, significantly higher cylinder wall velocities, plate velocities, and pressures were observed for the aluminum formulations at ≥2 μs. Additionally, hydrocode calculations were performed to determine how non‐ideal behavior affected the plate test results. Collectively, this work gives a clearer picture of how aluminum contributes to detonation on timescales from 1 μs to about 2 ms, and how the post‐detonation energy release contributes to wall velocities and blast effects. The experiments indicate that significant aluminum reactions occur after the CJ plane, and continue to contribute to expansion at late times.     

Visible‐near infrared concealment of cotton/nylon fabrics using colored pigments and multiwalled carbon nanotube particles (MWCNTs)

To match the reflectance profile of desert colors including dark brown, light brown and olive green in the visible‐near IR (Vis‐NIR) bands, five selected colored pigments were utilized to print woven cotton/nylon fabrics. Multi‐walled carbon nanotube particles (MWCNT's) were also added to some of the printing pastes. The reflectance of printed fabrics was evaluated by using spectrophotometric technique. The effect of adding MWCNT's, on washing; light and crocking fastness alongside with colorimetric values of printed samples was evaluated. Furthermore, the water absorption time was measured in order to determine wettability of each printed sample. The results demonstrated that the presence of MWCNT's in concentration range of 0.04–0.12 g kg^?1 in printing formulations was found to cause considerable decline in Near Infrared (NIR) reflectance while a surprising increase in visible reflectance of samples was observed. Color characteristics of printed fabrics were noticeably changed even at concentrations as low as 0.12 g kg^?1 MWCNTs in printing formulations. Presence of MWCNTs in printing formulations was found to cause a significant increase in wetting time of samples. Also, the results indicated that air permeability of printed samples containing MWCNT's were higher than samples printed with no MWCNTs. Phenomena imposed by MWCNT's presence on pigment printed samples showed very good fastness levels in crocking, washing and light fastness tests. In dark brown sample, adding MWCNTs to the pigment printing pastes could tune the overall reflectance in order to match the standard reflectance profile accepted for use in concealment color of desert areas. © 2013 Wiley Periodicals, Inc. Col Res Appl, 40, 93–98, 2015     

Drug‐release behavior of chitosan‐g‐poly(vinyl alcohol) copolymer matrix

Chitosan‐g‐poly(vinyl alcohol) (PVA) copolymers with different grafting percent were prepared by grafting water‐soluble PVA onto chitosan. The drug‐release behavior was studied using the chitosan‐g‐PVA copolymer matrix containing prednisolone in a drug‐delivery system under various conditions. The relationship between the amount of the released drug and the square root of time was linear. From this result, the drug‐release behavior through the chitosan‐g‐PVA copolymer matrix is shown to be consistent with Higuchi's diffusion model. The drug‐release apparent constant (K_H) was slightly decreased at pH 1.2, but increased at pH 7.4 and 10 according to the increasing PVA grafting percent. Also, K_H was decreased by heat treatment and crosslinking. The drug release behavior of the chitosan‐g‐PVA copolymer matrix was able to be controlled by the PVA grafting percent, heat treatment, or crosslinking and was also less affected by the pH values than was the chitosan matrix. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 458–464, 1999     

Retro‐Enantio N‐Methylated Peptides as β‐Amyloid Aggregation Inhibitors

An emerging and attractive target for the treatment of Alzheimer's disease is to inhibit the aggregation of β‐amyloid protein (Aβ). We applied the retro‐enantio concept to design an N‐methylated peptidic inhibitor of the Aβ42 aggregation process. This inhibitor, inrD, as well as the corresponding all‐L (inL) and all‐D (inD) analogues were assayed for inhibition of Aβ42 aggregation. They were also screened in neuroblastoma cell cultures to assess their capacity to inhibit Aβ42 cytotoxicity and evaluated for proteolytic stability. The results reveal that inrD and inD inhibit Aβ42 aggregation more effectively than inL, that inrD decreases Aβ42 cytotoxicity to a greater extent than inL and inD, and that as expected, both inD and inrD are stable to proteases. Based on these results, we propose that the retro‐enantio approach should be considered in future designs of peptide inhibitors of protein aggregation.     

Swelling mechanism of porous P(VP‐co‐MAA)/PNIPAM semi‐IPN hydrogels with various pore sizes prepared by a freeze treatment

BACKGROUND: The objective of the work reported was to investigate the effect of gel microstructure on the swelling mechanism. A series of porous gels with various pore sizes were prepared by freeze‐treating a conventional hydrogel that contained various amounts of water at ? 20 °C. Scanning electron microscopy and differential scanning calorimetry were used to characterize the microstructure of the porous gels. RESULTS: The experimental results showed that the water content during freezing was the key factor controlling the microstructure. Measurement of swelling kinetics showed that a greater amount of water during the freezing process would lead to a rapid swelling rate. The apparent diffusion coefficients (D_p) at all times during the swelling process were obtained by fitting the experimental data to the diffusion equation. The values of D_p suggested that the swelling mechanism of the gels depends on the pore size. The diffusion exponent (n) obtained by fitting the fractional mass change (M_t/M_∞) to equation of Fick's law further confirmed that the swelling mechanism of the gels is determined by the pore size. CONCLUSION: The swelling mechanism of the gels is determined by the microstructure related to the pore size and the thickness of struts. The microstructure can be controlled by adjusting the water content of the hydrogels by changing the pH of the swelling medium prior to freezing. Copyright © 2008 Society of Chemical Industry